JP2002517550A - Detergent containing amylase and color transfer inhibitor - Google Patents

Abstract

  (57) [Summary] It is an object of the present invention to improve the cleaning performance of detergents containing enzymes, especially with regard to starch-containing and colored stains. The object of the present invention is substantially solved by a detergent comprising an α-amylase from Bacillus amyloliquefaciens and a color transfer inhibitor together with other conventional components which are compatible with these components.

Description

DETAILED DESCRIPTION OF THE INVENTION

TECHNICAL FIELD The present invention relates to an enzyme-containing detergent containing an amylase derived from Bacillus amyloliquefaciens and a color transfer inhibitor together with ordinary components.

BACKGROUND OF THE INVENTION [0002] Laundry detergents typically contain other ingredients in addition to the laundry-active ingredients (eg, surfactants and builder materials). Such other components may be collectively referred to as cleaning aids and include different active groups such as foam control agents, stain inhibitors, bleaches, bleach activators and color transfer inhibitors. Such auxiliaries also include substances that aid in surfactant performance by enzymatically degrading soils present on textiles. This also applies, mutatis mutandis, to cleaning products for hard surfaces. Here, as well as proteases that assist in protein removal and lipases that degrade fat, amylase is also particularly important. Amylase has the function of promoting starch soil removal by catalytic hydrolysis of starch polysaccharides and has long been used in dishwashing detergents and textile laundry detergents for this purpose. In most cases, the amylase used consists of a thermostable amylase from Bacillus licheniformis, for example, which is commercially available under the name Termamyl®. More recently, genetically engineered amylases, ie, amylases whose amino acid sequence has been altered from naturally occurring amylase by genetic engineering methods, have been increasingly used in such compositions. The purpose of the genetically engineered amylase is to improve the performance and substantially improve the stability of the enzyme, especially the stability against attack by oxidizing agents. One way to achieve this goal is in International Patent Application WO 9
No. 4/18314, which discloses that amino acids highly susceptible to oxidation (
For example, methionine, tryptophan, cysteine or tyrosine) is removed from the amino acid sequence of the amylase, or other amino acids with higher oxidative stability are introduced instead of these amino acids. A similar method is described in International Patent Application WO 95/21247, which discloses at least one amino acid sequence in an amylase amino acid sequence.
It is recommended that one methionine be replaced with an amino acid that is neither methionine nor cysteine.

DISCLOSURE OF THE INVENTION Technical Problem Such genetic manipulation can improve the amylase stability under certain application conditions, but can be useful for washing or cleaning amylase-containing compositions. Amylase's contribution to cleaning performance does not improve.

[0004] Surprisingly, it has been surprisingly found that the combination of certain naturally occurring α-amylases with an anti-transfer agent results in unexpected synergistic performance improvements in detergents. That is, the present invention relates to an α-amylase derived from Bacillus amyloliquefaciens, a percarboxylic acid and / or an alkali metal salt thereof, and an amylase-containing detergent containing ordinary components compatible with such components.

The present invention also relates to the use of such a combination for improving the cleaning performance of detergents in detergent solutions, in particular aqueous detergent solutions, in particular with respect to starch soiling. The present invention provides a method for preventing the dyes of colored textiles from migrating in aqueous solutions (especially aqueous solutions containing surfactants) to undyed or differently colored textiles to be washed together. It also concerns the use of such combinations.

[0006] α-amylase derived from Bacillus amyloliquefaciens is disclosed in, for example, US Pat.
227374 has long been known. Such amylase is commercially available, for example, under the name Amylase BAN ™. The composition according to the invention contains amylolytic protein per gram of total composition, preferably in an amount of 0.001 to 0.5 mg, especially 0.02 to 0.3 mg.
Protein concentration can be determined by known methods, such as the bicinchoninic acid method (BCA method, Pierce C
chemical Co., Rockford, IL) or biuret method (AG Gornell, CS Bard)
awill and MM David, J. Biol. Cham. 177 , 751-766, 1948).

The detergent of the present invention preferably contains 0.1 to 2% by weight, especially 0.1% by weight of a color transfer inhibitor.
It contains 2 to 1% by weight. In a preferred embodiment of the present invention, the color transfer inhibitor,
It is a polymer of vinylpyrrolidone, vinylimidazole, vinylipyridine-N-oxide or a copolymer thereof. Useful color transfer inhibitors are exemplified by: polyvinylpyrrolidone with a molecular weight of 15,000 to 50,000, known from European Patent Application EP 0 262 897; German Patent Application DE 281287 or DE 38036
30 or International Patent Applications WO94 / 10281, WO94 / 26796, WO9
N-vinylimidazole / N-vinylpyrrolidone copolymers known from 5/03388 and WO 95/03382, polyvinyloxazolidones known from German Patent Application DE 28 14 329, copolymers derived from vinyl monomers and carboxamides known from European Patent Application EP610846, International Patent Application Pyrrolidone group-containing polyesters and polyamides known from WO 95/09194, graft polyamidoamines and polyethylene imines known from international patent application WO 94/29422, amide group-containing polymers derived from secondary amines known from German patent application DE 4328254, international patents Application W
O94 / 02579 or polyamine-N-oxide polymers known from European Patent Application EP 0 135 217, polyvinyl alcohols known from European Patent Application EP 0 847 838, and copolymers derived from acrylamidoalkenyl sulfonic acids known from European Patent Application EP 0584709.

However, an enzyme system consisting of peroxidase and hydrogen peroxide or a substance that produces hydrogen peroxide in water (for example, International Patent Applications WO 92/18687 and WO 91
/ 05839) may be used. In this case, a mediator compound for peroxidase, such as acetosyringone known from International Patent Application WO 96/10079, a phenol derivative known from International Patent Application WO 96/12845, or a phenothiazine or phenoxazine known from International Patent Application WO 96/12846, is used. Preferably, it is added, but the color transfer inhibitor polymer may be added. The polyvinylpyrrolidone used in the detergents according to the invention preferably has an average molecular weight of 10,000 to 60,000, especially 25,000 to 50,000. In the case of copolymers, 5000 to 50,000, especially 100
Preference is given to copolymers of vinylpyrrolidone and vinylimidazole in a molar ratio of from 5: 1 to 1: 1 having an average molecular weight of from 00 to 20,000.

In addition to the active substance combinations used according to the invention, the detergents according to the invention (solids,
In particular, it may be present as a powdery solid, as later compacted particles, or as a homogeneous solution or suspension), which may in principle contain any known ingredients normally present in such compositions. The compositions according to the invention are, inter alia, builder materials, surfactants, bleaching agents based on further organic and / or inorganic peroxygen compounds, bleaching activators, water-miscible organic solvents, further enzymes, sequestration. Agents, electrolytes, pH regulators, and other auxiliaries, such as optical brighteners, stain inhibitors, foam regulators, dyes and fragrances may be included.

The compositions of the present invention may contain one or more surfactants, suitable surfactants include anionic surfactants, nonionic surfactants, mixtures thereof, and cationic surfactants. Includes zwitterionic and amphoteric surfactants.

Suitable nonionic surfactants are, inter alia, alkyl glycosides and ethoxylated and / or propoxylated alkyl glycosides or linear or branched alcohols (C 12-18 alkyl moiety, alkyl ether group 3). To 12, preferably 4 to 10). N-alkylamines, vicinal diols, fatty acid esters and fatty acid amides (corresponding to the long-chain alcohol derivatives for the alkyl moiety), and alkylphenols (alkyl groups having 5 carbon atoms)
The corresponding ethoxylated and / or propoxylated compounds of ル 12) can also be used.

Preferred nonionic surfactants are alkoxylated (preferably ethoxylated)
Particularly preferred are primary alcohols which comprise alcohols having 8 to 18 carbon atoms and an average of 1 to 12 moles of ethylene oxide (EO) per mole of alcohol, wherein the alcohol residues are linear or preferably 2- It may be methyl-branched and / or have a mixture of straight-chain and methyl-branching groups as in normal oxo alcohol residues. However, C _12-18 alcohols of natural origin (eg coconut oil alcohol, palm oil alcohol, tallow alcohol or oleyl alcohol)
Alcohol ethoxylates having a linear group of 2 and an average of 2 to 8 EO per mole of alcohol are particularly preferred. Preferred ethoxylated alcohols are, for example, C _{12-1 4} alcohol + 3EO or 4 EO, C _9-11 alcohol + 7EO, C _13-15 alcohol + 3EO, 5EO, 7EO or 8EO, C _12-18 alcohol + 3EO, 5
EO or 7EO include, and mixtures thereof (for example mixtures of C _12-14 alcohol + 3EO and C _12-18 alcohol + 7EO). The degree of ethoxylation is a statistical average that can be integer or non-integer depending on the product. Alcohol ethoxylates with a narrow homolog distribution (narrow range ethoxylates, NRE) are preferred. In addition to such nonionic surfactants, fatty alcohols with EO greater than 12 may also be used. Examples are (tallow) fatty alcohols + 14EO, 16EO, 2
0EO, 25EO, 30EO or 40EO.

Particularly in detergents used for machine dishwashing, very low foaming compounds are usually used. Such compounds preferably include _C12-18 alkyl polyethylene glycol polypropylene glycol ethers having up to 8 moles each of ethylene oxide and propylene oxide units in the molecule. However, with ethylene oxide units and butylene oxide units up to 8 mol, respectively in addition to nonionic surfactants which are known to be low-foaming, for example C _{12-1 8} alkyl polyethylene glycol polybutylene glycol ethers (molecular ), And end-capped alkyl polyalkylene glycol mixed ethers can also be used. As described in European Patent Application EP0300305,
Hydroxyl-containing alkoxylated alcohols (referred to as hydroxy mixed ethers) are particularly preferred.

[0014] Alkyl glycosides represented by the formula RO (G) x are also included in the nonionic surfactant. In the formula, R is a primary linear or methyl-branched (particularly 2-methyl-branched) aliphatic group having 8 to 22 carbon atoms, preferably 12 to 18 carbon atoms, and G is 5 or 6 carbon atoms.
Of glucose units (preferably glucose). The degree of oligomerization x indicates the distribution of monoglycosides and oligoglycosides, and is 1 to 10, preferably 1.2 to 1.2.
It is a number of 1.4 (the value may not be an integer as a statistically determined value).

[0015] Other suitable surfactants are of formula (II):

Embedded image [Wherein, R ¹ CO is an aliphatic acyl group having 6 to 22 carbon atoms, R ² is hydrogen, an alkyl or hydroxyalkyl group having 1 to 4 carbon atoms, and [Z] is a 3 to 10 carbon atoms.
/ A straight-chain or branched polyhydroxyalkyl group having 3 to 10 hydroxyl groups. ] It is a polyhydroxy fatty acid amide shown by these. The polyhydroxy fatty acid amide is preferably derived from a reducing sugar having 5 or 6 carbon atoms, especially glucose.

The group of polyhydroxy fatty acid amides has the formula (III):

Embedded image [In the formula, R ³ is a straight-chain or branched alkyl or alkenyl group having 7 to 12 carbon atoms, and R ⁴ is a straight-chain, branched or cyclic alkylene group having 2 to 8 carbon atoms or arylene. R ⁵ is a linear, branched or cyclic alkyl or aryl or oxyalkyl group having 1 to 8 carbon atoms, preferably a C _1-4 alkyl group or a phenyl group, and [Z] Is a linear polyhydroxyalkyl group having an alkyl chain substituted by at least two hydroxyl groups, or an alkoxylated (preferably ethoxylated or propoxylated) derivative thereof. ] It also includes the compound shown by these. Again, preferably [Z] is derived by reductive amination of a sugar such as glucose, fructose, maltose, lactose, galactose, mannose or xylose. The N-alkoxy- or N-aryloxy-substituted compounds are then converted, for example, from the international patent application WO 95/0.
Reaction with fatty acid methyl esters in the presence of an alkoxide as a catalyst according to 7331 can convert to the desired polyhydroxy fatty acid amide.

Other preferred nonionic surfactants for use as the only nonionic surfactant or in combination with other nonionic surfactants, especially alkoxylated fatty alcohols and / or alkyl glycosides, are fatty acids Alkoxylates, especially ethoxylated or ethoxylated / propoxylated alkyl esters (preferably having 1 to 4 carbon atoms in the alkyl chain), especially fatty acid methyl esters, which are described, for example, in Japanese Patent Application JP 58/217598. Or preferably prepared by the method described in International Patent Application WO 90/13533.

Nonionic surfactants of the amine oxide type, for example N-cocoalkyl-N,
Also suitable are N-dimethylamine oxide and N-tallow alkyl-N, N-dihydroxyethylamine oxide, and nonionic surfactants of the fatty acid alkanolamide type. The amount of such nonionic surfactant preferably does not exceed the amount of ethoxylated fatty alcohol, more preferably not more than half.

Other suitable surfactants include those known as so-called Gemini surfactants. Gemini surfactant usually means a compound having two hydrophilic groups per molecule. The groups are usually separated from one another by so-called spacers. Spacers are typically carbon chains that should have a length sufficient to separate the hydrophilic groups so that they can function independently of one another. Gemini surfactants are typically characterized by very low critical micelle concentrations and the ability to significantly reduce the surface tension of water. Gemini surfactants may include not only dimeric surfactants, but also trimer surfactants.

Examples of suitable gemini surfactants are sulphated hydroxy mixed ethers according to German Patent Application DE43221022, or dimeric alcohol bis- and trimer alcohol tris-sulphate and -ether sulphate according to German Patent Application DE 19503061. is there. The end-capped dimeric and trimeric mixed ethers according to German Patent Application DE 195 13 391 are characterized, inter alia, by their bifunctional and multifunctional nature. That is, such end-cap surfactants are particularly suitable for use in mechanical washing or cleaning methods because they exhibit good wettability and low foaming properties. International Patent Applications WO95 / 19953, WO95
Gemini polyhydroxy fatty amides or poly polyhydroxy fatty acid amides described in WO 95/19955 and WO 95/19955 may be used.

Suitable anionic surfactants are, inter alia, soaps and sulfates or salts.
It has a sulfonate group. Preferred surfactants of the sulfonate type are C _9-13 Alkylbenzenesulfonates, olefinsulfonates, i.e.
Having terminal or non-terminal double bonds_12-18Monoolefin is converted to gaseous trioxide
Sulfonate with au, then alkali or acid hydrolyze the sulfonated product
Alkene sulfonate and hydroxyalkane sulfo
It is a mixture of catenate and disulfonate. C_12-18From alkanes, for example
By ruhochlorination or sulfoxidation followed by hydrolysis or neutralization
The resulting alkane sulfonates are also suitable.

Also suitable are esters of α-sulfo fatty acids (ester sulfonates), such as α-sulfonated methyl esters of fatty acids of hydrogenated coconut oil, palm kernel oil or tallow. This is obtained by α-sulfonating a methyl ester of a fatty acid derived from plants and / or animals (having 8 to 20 carbon atoms in the fatty acid molecule) and then neutralizing it into a water-soluble monosalt. Such esters are preferably hydrogenated coconut oil, palm oil, palm kernel oil or α-sulfonated esters of fatty acids of tallow, but also small amounts of sulfonated unsaturated fatty acids (eg oleic acid), preferably about 2-3% by weight
Below) may be present. Particularly preferred are α-sulfofatty acid alkyl esters having an alkyl chain having 4 or less carbon atoms in the ester group (eg, methyl ester, ethyl ester, propyl ester and butyl ester). It is particularly advantageous to use α-sulfofatty acid methyl ester (MES) and its saponified disalt.

Other suitable anionic surfactants are sulfated fatty acid glycerol esters, ie, monoglycerol is esterified with 1-3 moles of fatty acids, or triglyceride is esterified with 0.3-2 moles of glycerol. Mono-, di- and triesters obtained by exchange and mixtures thereof.

Preferred alkyl (alkenyl) sulfates are C _12-18 fatty alcohols, such as coconut oil fatty alcohol, tallow fatty alcohol, lauryl, myristyl, cetyl or stearyl alcohol, or the sulfuric monoester of C _10-20 oxo alcohol, and Of a sulfuric acid monoester of a secondary alcohol having a similar chain length,
Alkali metal salts, especially sodium salts. Another preferred alkyl (alkenyl) sulfate is an alkyl (alkenyl) sulfate having the above-mentioned chain length having a synthetic linear alkyl chain derived from petrochemicals, which has a degradability comparable to the corresponding compound derived from a fat and oil chemical raw material. Have C _12-16 alkyl sulfate, C _12-15 alkyl sulfate, and C _14-15 alkyl sulfate are particularly preferred in terms of cleaning performance.

Another suitable anionic surfactant is a 2,3-alkyl sulphate, which can be prepared, for example, according to US Pat. No. 3,234,258 or US Pat.
Commercially available from the Oil Company under the name DAN ™. Ethylene oxide 1
Ethoxylated with 6 mol of the straight-chain or branched C _7-21 alcohols, such as 2-methyl-branched C _9-11 alcohols + average of 3.5 moles EO (ethylene oxide) or C _12-18 fatty alcohol + 1～4EO Sulfuric acid monoesters are also suitable.

Preferred anionic surfactants are also sulfosuccinates or sulfosuccinates, which are monoesters and / or diesters of sulfosuccinic acids with alcohols (preferably fatty alcohols, more preferably ethoxylated fatty alcohols). It also includes the known salts of alkylsulfosuccinic acids. Preferred sulfosuccinates have _C8-18 fatty alcohol residues or mixtures thereof.
Particularly preferred sulfosuccinates have fatty alcohol groups derived from ethoxylated fatty alcohols, which are themselves nonionic surfactants. Sulfosuccinates having fatty alcohol groups derived from ethoxylated fatty alcohols with a narrow homolog distribution are particularly preferred. Preferably 8 to 1 in the alkyl (alkenyl) chain
Alkyl (alkenyl) succinic acids having 8 carbon atoms or salts thereof may be used.

[0027] Other suitable anionic surfactants include fatty acid derivatives of amino acids, such as fatty acid derivatives of N-methyltaurine (tauride) and / or N-methylglycine (sarcoside). Sarcosides and sarcosinates, especially sarcosinates of higher mono- or polyunsaturated fatty acids (eg oleyl sarcosinate) are particularly preferred.

Other suitable anionic surfactants are, inter alia, soaps. Suitable soaps are, inter alia, saturated fatty acid soaps, such as salts of lauric acid, myristic acid, palmitic acid, stearic acid, hydrogenated erucic acid and behenic acid, and especially natural fatty acids (for example coconut oil fatty acids, palm kernel oil fatty acids or tallow fatty acids). )). Known alkenyl succinates may be used with or instead of such soaps.

[0029] Anionic surfactants (including soaps) can be present in the form of sodium, potassium or ammonium salts and in the form of soluble salts with organic bases such as mono, di or triethanolamine. The anionic surfactant is preferably in the form of a sodium or potassium salt, with the sodium salt being particularly preferred.

The surfactant in the laundry detergent according to the invention is preferably 5 to 50% by weight, especially 8%.
It is present in an amount of ３０30% by weight. Compositions for hard surface cleaning, especially for mechanical cleaning of kitchenware and tableware, have a lower surfactant content, up to 10% by weight, especially up to 5% by weight, preferably from 0.5 to 3%. % By weight.

The composition according to the invention preferably contains at least one water-soluble and / or water-insoluble organic and / or inorganic builder. Water-soluble organic builder materials include: polycarboxylic acids, especially citric and sugar acids, aminopolycarboxylic acids in monomeric and polymeric form, especially methylglycine diacetate, nitrilotriacetic acid and ethylenediaminetetraacetic acid, polyasparagine. Acids, polyphosphonic acids, especially aminotris (methylenephosphonic acid), ethylenediaminetetrakis (methylenephosphonic acid) and 1-hydroxyethane-1,1-diphosphonic acid,
Hydroxy compounds in polymeric form, for example dextrins, (poly) carboxylic acids in polymeric form, in particular European Patent EP 0 625 992 or International Patent Application WO 92 /
18542 or the polymers of polycarboxylates, acrylic acid, methacrylic acid or maleic acid and their copolymers which can be obtained by oxidizing polysaccharides or dextrins according to EP 0 232 2022 (a small amount of polymerizable material without carboxylic acid function May be copolymerized). The relative molecular weight of the homopolymer of the unsaturated carboxylic acid is usually 3,000 to 200,000, and the relative molecular weight of the copolymer is 2,000 to 200,000, preferably 30,000 to 12,000.
0 (in terms of free acid). Particularly preferred acrylic / maleic acid copolymers are
It has a relative molecular weight of 30,000-100,000. Examples of commercial products are Sokalan (
Trademarks) CP5, CP10 and PA30 (BASF). Less preferred, but less preferred, compounds of this class are copolymers of acrylic or methacrylic acid with vinyl ethers (eg, vinyl methyl ether), vinyl esters, ethylene, propylene and styrene, wherein the acid moiety Is at least 50
% By weight.

Terpolymers comprising, as suitable water-soluble organic builder materials, two unsaturated acids and / or their salts as monomers and vinyl alcohol and / or esterified vinyl alcohol or carbohydrates as third monomers May be used. The first acidic monomer or its salt, monoethylenically unsaturated C _3-8 carboxylic acid, preferably derived from C _3-4 monocarboxylic acids (especially acrylic acid or methacrylic acid). The second acidic monomer or salt thereof may be a derivative of C _4-8 dicarboxylic acid (maleic acid is particularly preferred) and / or a derivative of allylsulfonic acid substituted at the 2-position with an alkyl or aryl group. Such polymers are described, inter alia, in German Patent DE 4221381 and German Patent Application DE
No. 4,300,772, typically from 1000 to 2
It has a relative molecular weight of 00000. Other preferred copolymers are the copolymers described in German Patent Applications DE4303320 and DE4417734, which preferably contain acrolein and acrylic acid / acrylate and / or vinyl acetate as monomers. Especially for the production of liquid compositions,
The organic builder material may be used in the form of an aqueous solution, preferably a 30-50% by weight aqueous solution. All the above-mentioned acids are usually used in the form of their water-soluble salts, especially the alkali metal salts.

If desired, organic builder materials of this kind can be present in an amount of up to 40% by weight, especially 25
It can be present in an amount up to% by weight, preferably 1-8% by weight. It is preferable to use an amount close to the above-mentioned upper limit for the paste or liquid composition of the present invention (particularly, one containing water).

Suitable water-soluble inorganic builder materials include, inter alia, alkali metal silicates, alkali metal carbonates and alkali metal phosphates, which may be present in the form of alkaline, neutral or acidic sodium or potassium salts. Examples are trisodium phosphate, tetrasodium diphosphate, disodium dihydrogen diphosphate, pentasodium triphosphate, so-called sodium hexametaphosphate, trisodium phosphate oligomers (oligomerization degree 5 to 1000, especially 5 to 1000). 50), and the corresponding potassium salts and / or mixtures of sodium and potassium salts. The water-insoluble, water-dispersible inorganic builder material is, inter alia, a crystalline or amorphous alkali metal aluminosilicate in an amount of up to 50% by weight, preferably up to 40% by weight, especially 1 to 5% by weight in the liquid composition. Use in% amount. Among such inorganic builders, crystalline sodium sodium aluminosilicate for detergents, in particular zeolites A, P and optionally X, alone or as a mixture (for example a co-crystal of zeolites A and X (Vegobond ™ AX, Condea Augusta SpA). In the solid particulate composition, it is preferable to use an amount near the upper limit of the above range. In suitable aluminosilicates, in particular, no particles having a size greater than 30 μm are present, preferably particles smaller than 10 μm make up at least 80% by weight. Its calcium binding capacity is usually
100-200 mg CaO / g (can be determined according to DE 2412837).

Suitable replacements or partial replacements for the above aluminosilicates include:
A crystalline alkali metal silicate, which may be present alone or as a mixture with an amorphous silicate. The alkali metal silicate which can be used as a builder in the composition of the present invention preferably has a molar ratio of alkali metal oxide to SiO ₂ of 0.1.
It is less than 95, especially from 1: 1.1 to 1:12, and may be present in amorphous or crystalline form. Preferred alkali metal silicates are Na ₂ O: Si
Sodium silicate with an O ₂ molar ratio of 1: 2 to 1: 2.8, especially amorphous sodium silicate. Those having a molar ratio of Na ₂ O: SiO ₂ of 1: 1.9 to 1: 2.8 can be prepared by the method of European Patent Application EP 0 425 427. Preferred crystalline silicates, which may be present alone or in a mixture with an amorphous silicate, are
_{Formula: Na 2 Si x O 2x +} 1 · yH in ₂ O [wherein, x (the so-called modulus) is 1.9
22, especially 1.9 to 4, y is a number from 0 to 33, and x is preferably 2
, 3 or 4. ] Is a crystalline layered silicate represented by the formula: The crystalline layered silicate represented by the above formula is described, for example, in European Patent Application EP 0164514. In the formula, a crystalline layered silicate in which x is 2 or 3 is preferable. β- and δ-sodium disilicate (Na ₂ Si ₂ O ₅ .yH ₂ O) are particularly preferred. β-Sodium disilicate can be obtained, for example, by the method described in International Patent Application WO 91/08171. Δ-Sodium silicate having a modulus of 1.9 to 3.2 is
It can be prepared according to Japanese Patent Applications JP04 / 238809 and JP04 / 260610. A substantially anhydrous crystalline alkali metal silicate represented by the above formula wherein x is 1.9 to 2.1 (European Patent Applications EP0548599, EP050232)
5 and prepared from an amorphous alkali metal silicate, which can be prepared as described in EP 0 452 428) may be used in the compositions of the present invention.

In another preferred embodiment of the composition according to the invention, reference is made to European patent application EP04368.
A crystalline layered sodium silicate with a modulus of 2-3, which can be prepared from sand and soda by the method of 35, is used. In another preferred embodiment of the composition according to the invention, use is made of crystalline sodium silicate with a modulus of 1.9 to 3.5, obtainable by the method of EP 0 164 552 and / or EP 0 293 753.

The crystalline layered silicate represented by the above formula is obtained from Clariant GmbH as Na-SKS, for example, N
a-SKS-1 (Na ₂ Si ₂₂ O ₄₅・ xH ₂ O, kenyaite), Na-SKS-2 (Na ₂ Si ₁₄ O ₂₉・ xH ₂ O, magadiit
e), Na-SKS-3 (Na 2 Si 8 O 17 · xH 2 O) or _{Na-SKS-4 (Na 2} Si 4 O 9 · xH 2 O, which is commercially available under the trade name makatite). Among them, particularly suitable ones are Na-SKS-5 (α-Na ₂ Si ₂ O ₅ ), Na-SKS-7 (β-Na ₂ Si ₂ O ₅ , natrosilite), Na-SKS-9 ( NaHSi ₂ O ₅ · The _{3H 2 O), N a-} SKS-10 (NaHSi 2 O 5 · 3H 2 O, kanemite), Na-SKS-11 (t-Na 2 Si 2 O 5) and Na-SKS
-13 (NaHSi ₂ O ₅ ), with Na-SKS-6 (δ-Na ₂ Si ₂ O ₅ ) being particularly important. For an overview of crystalline layered silicates, see, for example, "Hoechst High Chem Magazin 14/1993"
Pages 33-38 and "Seifen-Oele-Fette-Wachse, Vol. 116, No. 20/1990" No. 805-8
It is described on page 08. In a preferred embodiment of the composition according to the invention, a granular formulation of crystalline layered silicate and citrate, a granular formulation of crystalline layered silicate and the above-mentioned polycarboxylic acid (co) polymers (for example, German Patent Application DE 198)
19187), or a granulated blend of alkali metal silicate and alkali metal carbonate (eg as described in International Patent Application WO 95/22592 or commercially available as eg Nabion ™ 15) I do.

[0038] The builder material may be present in the composition of the present invention in an amount up to 90% by weight if desired. Preferably, the builder material is present in an amount up to 75% by weight. The builder content of the laundry detergent according to the invention is in particular from 5 to 50% by weight.

Suitable peroxygen compounds for the composition according to the invention are, in particular, organic peracids or persalts of organic acids, for example phthalimidopercaproic acid, perbenzoic acid or diperdodecane diacid, peroxides Includes hydrogen and inorganic salts that release hydrogen peroxide under scrubbing conditions, such as perborates, percarbonates, persilicates and / or persulfates (eg Caroate). If a solid peroxygen compound is used, it can be used in the form of a powder or granules, which can in principle be coated in a known manner. If the composition according to the invention contains a peroxygen compound, the peroxygen compound is preferably present in an amount of up to 50% by weight, more preferably 5 to 30% by weight. It may be advantageous to add small amounts of known bleach stabilizers such as phosphonates, borates and / or metaborates and metasilicates and magnesium salts (eg magnesium sulphate).

The bleaching activators which can be used, under perhydrolysis conditions, preferably have 1 to 10 carbon atoms.
More preferably, it is a compound that produces aliphatic peroxocarboxylic acid of 2-4) and / or substituted or unsubstituted perbenzoic acid. A substance having an O- and / or N-acyl group having the above carbon number and / or a substituted or unsubstituted benzoyl group is suitable. Preferred bleach activators are polyacylated alkylenediamines, especially tetraacetylethylenediamine (TAED), acylated triazine derivatives, especially 1,5-diacetyl-2,4-dioxohexahydro-1,3,5-triazine (DADHT). Acylated glycolurils, especially tetraacetylglycoluril (TAGU), N-acylimides, especially N-nonanoylsuccinimide (NOSI), acylated phenolsulfonates, especially n-nonanoyl or isononanoyloxybenzenesulfonate (n- or iso- -NOB
S), carboxylic anhydrides, especially phthalic anhydride, acylated polyhydric alcohols, especially triacetin, ethylene glycol diacetate, 2,5-diacetoxy-
2,5-dihydrofuran, enol ester (German Patent Application DE19661669)
3 and DE 196 16767), acetylated sorbitol and mannitol and / or their mixtures (SORMAN) (European Patent Application E
P0525239), acylated sugar derivatives, especially pentaacetylglucose (PAG), pentaacetylfructose, tetraacetylxylose and octaacetyllactose, acetylated (optionally N-alkylated)
Glucamine and gluconolactone, and / or N-acylated lactams such as N-benzoylcaprolactam (International Patent Application WO 94/27970, WO
94/28102, WO94 / 28103, WO95 / 00626, WO95 /
14759 and WO 95/17498). Hydrophilic substituted acylacetals (known from German Patent Application DE 196 16 770) and acyllactams (German Patent Application DE 196 16 770 and International Patent Application WO 9
5/14075). Conventional bleach activator combinations known from German Patent Application DE 44 43 177 may be used. Such bleach activators are used in conventional amounts, preferably in the presence of the aforementioned hydrogen peroxide producing bleach, preferably 0.5 to 10% by weight, more preferably 1 to 8% by weight, based on the total composition. % Can be used. However, when the percarboxylic acid essential for the present invention is used as the only bleaching agent, it is preferred that no bleaching activator is present.

In addition to or instead of conventional bleach activators, EP 044698
2 and / or transition metal salts or complexes having a bleach-enhancing action known from EP 0453003 can be present as so-called bleach catalysts.

In addition to the amylase essential for the present invention, enzymes that can be used in the composition of the present invention include:
Includes enzymes selected from the group consisting of proteases, lipases, cutinases, pullulanases, hemicellulases, cellulases, oxidases, lac enzymes and peroxidases and mixtures thereof. If desired, amylases other than the amylase essential for the present invention may be further used. Fungi or bacteria, such as Bacillus sub
tilis, Bacillus licheniformis, Bacillus lentus, Streptomyces griseus, Hu
micola lanuginosa, Humicola insolens, Pseudomonas pseudoalcaligenes, Pse
Active enzyme substances obtained from udomonas cepacia or Coprinus cinereus are particularly suitable. The amylases essential for the invention and the enzymes which can be further used are adsorbed on a carrier material and / or encapsulated in a coating material, for example as described in EP 0 564 476 or International Patent Application WO 94/23005. , Can be protected from premature deactivation. These are preferably present in the detergents of the invention in an amount of up to 5% by weight, more preferably 0.2-4% by weight.

When the composition of the present invention contains a protease, its proteolytic activity is preferably about 100 to 10,000 PU / g, especially 300 to 8000 PU / g. If two or more enzymes are used in the composition according to the invention, two or more individual enzymes or enzymes which are conventionally individually formulated may be combined, or may be combined, for example, from International Patent Application WO 96 / 00772 or WO96 /
Granules formulated by combining two or more enzymes as known by 00773 may be used.

Organic solvents which can be used besides water in the compositions according to the invention (especially when in liquid or paste form) include C _1-4 alcohols (especially methanol, ethanol, isopropanol and t-butanol), C _{Includes 2-4} diols (especially ethylene glycol and propylene glycol) and mixtures thereof, as well as ethers derived from the above classes of compounds. Such water-miscible solvents are present in the compositions of the present invention preferably in an amount of up to 30% by weight, more preferably in an amount of from 6 to 20% by weight.

In order to achieve a desired pH value which is not automatically adjusted by the mixing of the other components, the compositions of the present invention must be compatible with the system and with the environment-friendly acids (particularly citric acid, acetic acid, tartaric acid, It may contain malic acid, lactic acid, glycolic acid, succinic acid, glutaric acid and / or adipic acid) or an inorganic acid (especially sulfuric acid) or a base (especially ammonium hydroxide or alkali metal hydroxide). Such pH
The modifier is preferably present in the composition according to the invention in an amount up to 20% by weight, more preferably in an amount from 1.2 to 17% by weight.

The function of the antifouling agent is to keep the dirt separated from the textile fibers suspended in the liquid. Suitable for this purpose are water-soluble and usually organic colloids, such as starch, glue, gelatin, salts of ether carboxylic acids or ether sulfonic acids of cellulose or starch, or salts of acidic sulphates of cellulose or starch. Water-soluble polyamides having acid groups are also suitable. Other starch derivatives, such as aldehyde starch, may be used. Cellulose ethers, such as carboxymethylcellulose (sodium salt), methylcellulose, hydroxyalkylcellulose, mixed ethers (eg, methylhydroxyethylcellulose, methylhydroxypropylcellulose, methylcarboxymethylcellulose), and mixtures thereof, may be added to the composition at, for example, 0.1. It is preferably used in an amount of up to 5% by weight.

The laundry detergent of the present invention may contain a derivative of diaminostilbene disulfonic acid and / or an alkali metal salt thereof as a fluorescent whitening agent. Suitable optical brighteners are
For example, a salt of 4,4'-bis- (2-anilino-4-morpholino-1,3,5-triazinyl-6-amino) -stilbene-2,2'-disulfonic acid, or a similar structure having morpholino A compound having a diethanolamino group, a methylamino group, an anilino group or a 2-methoxyethylamino group instead of a group. Brighteners of the substituted diphenylstyryl type, for example 4,4'-bis- (2-sulfostyryl) -biphenyl, 4,4'-bis- (4-chloro-3-sulfostyryl) -biphenyl or 4- (
An alkali metal salt of 4-chlorostyryl) -4 '-(2-sulfostyryl) -biphenyl may be used. Mixtures of the above whitening agents may be used.

It may be advantageous to add customary foam inhibitors, especially when the compositions according to the invention are used for mechanical cleaning. Examples of suitable foam inhibitors are soaps of natural or synthetic origin with a high C _18-24 fatty acid fraction content. Suitable non-surfactant defoamers are, for example, organopolysiloxanes and mixtures thereof with fine, optionally silanized silica, and paraffins, waxes, microcrystalline waxes and silanized silica or bis-fatty alkylenediamines therewith. Is a mixture with It is also advantageous to use mixtures of various foam inhibitors, for example mixtures of silicones, paraffins or waxes. It is preferred that the foam inhibitor, especially a foam inhibitor containing silicone and / or paraffin, be immobilized on a granular water-soluble or water-dispersible support material. Mixtures of paraffin and bisstearylethylenediamine are particularly preferred.

The preparation of the solid compositions according to the invention can be carried out without difficulty and in a known manner, for example by spray-drying or granulation, with enzymes and other heat-sensitive components (eg bleaching agents) Add separately at the stage. High bulk density (especially 650-950
The compositions of the invention having a g / l range) are preferably prepared by a process comprising an extrusion process known from EP 0 486 592. Another preferred process is by the granulation process described in EP 0 624 576.

The present invention in tablet form, which may have one or more phases and may have one or more colors, especially tablet forms having one or two or more layers (especially two layers) To produce the composition, all the components (optionally layer by layer) are mixed in a mixer and the mixture is compressed with a conventional tablet press (eg, an eccentric press or a rotary press) with a compression force of about 50-100 kN (preferably (60-70 kN). Particularly in the case of multilayer tablets, it may be advantageous to pre-compress at least one layer. This is preferably 5-20 kN, especially 10-1
Performed with a compression force of 5 kN. In this way, the breaking strength and the bending strength are typically 100
Tablets that are resistant to rupture but dissolve quickly enough under the application conditions, up to 200 N, preferably more than 150 N, can be produced without problems. The weight of the tablets thus produced is preferably between 10 and 50 g, especially between 15 and 40 g. The three-dimensional shape of the tablet is optional and may be circular, oval or rectangular, and may be intermediate. Advantageously, the corners and edges are rounded. The diameter of the round tablet is preferably between 30 and 40 mm. In particular, mainly weighing devices (eg for dishwashers)
The size of the rectangular or cubic tablet to be introduced depends on the shape and volume of the metering device. In a preferred example, the bottom surface is (20 to 30 mm) × (34 to
40 mm), especially 26 × 36 mm or 24 × 38 mm.

The detergents according to the invention in liquid or paste form, usually in the form of a solution containing a solvent, are usually prepared by simply mixing the components which can be introduced as such or in the form of a solution into an automatic mixer.

────────────────────────────────────────────────── ─── Continuing on the front page (72) Inventor Horst-Dieter Speckmann Germany-Day 4067 Langenfeld, Eichenfeldstraße 24th (72) Inventor Karl-Heinz Maurer Germany-Day 40406 Erkler D, Dechenstrasse No. 5 F term (reference) 4H003 DA01 DA19 DB01 EB28 EC01 EC03 EE04 FA06 FA08 FA16 FA47

Claims (11)

[Claims] An amylase-containing detergent containing an α-amylase derived from Bacillus amyloliquefaciens, a color transfer inhibitor, and a usual component compatible with such a component. 2. An amount of amylase of 0.001 to 0.5 mg per 1 g of the whole detergent,
Detergent according to claim 1, especially containing in an amount of 0.02 to 0.3 mg. 3. The detergent according to claim 1, comprising 0.1 to 2% by weight of a color transfer inhibitor. 4. A color transfer inhibitor comprising vinyl pyrrolidone, vinyl imidazole,
The detergent according to any one of claims 1 to 3, which is a polymer of vinylpyridine-N-oxide or a copolymer thereof. 5. A color transfer inhibitor comprising 10,000 to 60,000, especially 250
A polyvinylpyrrolidone having an average molecular weight of 00 to 50,000.
5. The detergent according to any one of 4. 6. The anti-transfer agent according to claim 6, wherein said anti-transfer agent is from 5,000 to 50,000, especially 1,000.
5. The detergent according to claim 1, which is a copolymer of vinylpyrrolidone and vinylimidazole in a molar ratio of 5: 1 to 1: 1 having an average molecular weight of 0 to 20,000. 7. The detergent according to claim 1, wherein the color transfer inhibitor is a system comprising peroxidase and hydrogen peroxide and / or a substance that produces hydrogen peroxide in water. 8. The detergent according to claim 7, wherein the system further comprises a mediator compound for peroxidase. 9. The detergent according to claim 7, wherein the system further comprises a polymer of vinylpyrrolidone, vinylimidazole, vinylpyridine-N-oxide or a copolymer thereof. 10. Use of a combination of an α-amylase from Bacillus amyloliquefaciens and an anti-transfer agent for improving the cleaning performance of a detergent in a cleaning and cleaning solution, especially in an aqueous cleaning and cleaning solution, with respect to starch soiling. . 11. An aqueous solution of a combination of α-amylase derived from Bacillus amyloliquefaciens and an anti-color transfer agent, particularly in an aqueous solution containing a surfactant,
Use of the pigments of the colored textiles to avoid migrating to textiles that are unpigmented or have a different color to wash together.